Granular enzyme-containing laundry composition



United States Patent ABSTRACT OF THE DISCLOSURE Powdered enzymes, whichare cleaning aids, are attached to granular carriers which comprisepartially-hydrated hydratable salts such as sodium tripolyphosphate. Theattachment is done in the presence of water which effects the partialhydration. The granular carrier with the attached enzyme is useful inpre-wash soaking and in conjunction with detergent compositions.

CROSS REFERENCE This application is a continuation-in-part of copendingapplication Ser. No. 544,705 filed Apr. 25, 1966, now

abandoned, and copending application filed Mar. 6, 1967, now abandoned.

FIELD OF INVENTION This invention relates to a laundry compositioncomprising a powdered enzyme attached to a granular carrier which isbased on an hydratable salt. The invention also relates to a method forattaching powdered enzyme to the granular carrier.

Ser. No. 620,603

PRIOR ART AND PROBLEMS CONNECTED THEREWITH Laundry products containingenzymes are old. See, for

example, US. Patent 1,882,270, Frelinghusen, Oct. 11,

1932. Enzymes aid. in laundering by attacking soil and stains found onsoiled fabrics. Soils and stains are decomposed or altered in such anattack so as to render :them more removable during laundering. Enzymescan be used either in a soaking or pre-wash product designed .to preparesoiled fabric for more effective detergency when the fabrics aresubjected to conventional laundering, or as a component of a detergentformulation containing conventional cleaning ingredients. The enzymessuitable for such laundry uses are usually found in a fine powder form.Enzymes areexpensive and powerful ma terials which must be judiciouslyformulated and used.

Such fine powders of concentrated materials are difficult to handle,difficult to measure and difficult to formulate.

Prior art enzyme-containing laundry products are mechanical mixtures ofa fine enzyme powder and other granular materials. Enzyme powder in suchmechanical .mixtures tends to segregate, resulting in a non-uniformproduct. Nonuniformity results in an undependable product in use,particularly for measurement purposes. Such mechanical mixtures alsopresent stability problems resulting from the mobility of the enzymepowder in the mixture; it is exposed to some cleaning ingredients andenvironmental condition which may either attack the enzyme or aid it indegrading itself. For example, moisture.

tends to cause the enzyme to degrade itself; many enzymes areincompatible with highly alkaline detergent materials such as causticsoda, particularly in the presence .of moisture.

3,451,935 Patented June 24, 1969 'ice The granular laundry compositionof this invention comprises a powdered enzyme attached to a granularcarrier which overcomes the disadvantages associated with the prior artproducts. The granular carrier comprises a partially-hydrated hydratablesalt. The process of this invention is the application of powderedenzyme to such a granular carrier in the presence of water.

DETAILED DESCRIPTION The enzyme powder is attached to a granular carriercomprising a partially-hydrated hydratable .salt having a pH in therange of 4 to 12. The close association involved in such attachmenttends to isolate the enzyme powder from other materials used in anenzyme-containing prod uct which might be unfavorable to the enzyme froma stability or activity standpoint. Enzyme activity is its ability toperform the desired function of soil attack. Enzyme stability is itsability to remain in an active state. The attachment of the enzymepowder to the larger carrier granules overcomes segregation problems ofthe prior art mechanical mixtures.

In the compositions of this invention, the salt employed in or as thegranular carrier must be water-soluble and in a hydratable state toachieve the desired physical attachment characteristics and stabilityadvantages. The enzyme powder it attached to the granular carrier in thepresence of water, the water usually being used as the vehicle for theenzyme powder while attachment is being effected. The contact of thegranular" carrier by enzyme powder in the presence of Water results inreceipt of the water by the hydratable salt in the carrier in such a Waythat the enzyme powder is drawn on and attached to the surface of thecarrier granules in a blotter-like or spongelike action, leaving dryenzyme powder on the surface of the granules. To the extent that theenzyme applied to the carrier is dissolved in the water, some enzyme canbe drawn into the granular carrier and attached therewith as well asthereon.

The water taken up by the granular carrier in the at tachment processresults in partial hydration of the hydratable salt short of fullhydration. The remaining increment of hydratability of the hydratablesalt permits any free moisture associated with the laundry compositionof the invention, which might otherwise tend to cause degradation of theattached enzyme powder, to be received into the hydratable salt of thegranular carrier as additional water of hydration. Water so received isnot in contact with the enzyme to an extent significant enough to causedegradation thereof. This provides a much more favorable stabilitysituation for the laundry composition which contains the enzyme andgranular carrier.

While modern laundry products and detergent compositions are wellpackaged, they are often exposed to humidity initially in the package orafter the package is opened and the contents are being periodicallyused. The compositions of this invention have, by virtue of theattachment of the powdered enzyme to the granular carrier, stabilitycharacteristics that are markedly superior to the mechanical mixtures ofthe prior art where the enzyme powder is mobile and exposed.

HYDRATABLE SALTS Water-soluble hydratable salts employed as or in thegranular carrier of the compositions of this invention have certaincharacteristics relative to pH and hydration characteristics. As used inthe specification and claims the term hydratable salt defines onecompound of the desired properties or a mixture of such compounds.

Both the granular carrier and the hydratable salt used thereas ortherein should provide a pH in water solution in the range of from 4-12.Carrier granules and hydratable salt having pH values from 4-7 areprovided when the particular powdered enzyme chosen for attachment tothe granular carrier prefers an acidic environment for optimum activityand stability. Neutral or slightly alkaline pHs of 7-8 are employed foranalagous reasons. Granular carrier and hydratable salts providing pHsin the range of 4-8 generally function solely as a carrier for thepowdered enzyme. When the granular carrier, and the hydratable salt usedtherein, function as a detergent or a detergent component in addition toa carrier for the powdered enzyme, materials providing high pHs in the4-12 range are used, preferably in the range of 8-11. Water-solublehydratable builder salts, serving as or in a granular carrier ashereinafter described, either in granular form per se or as a portion ofa muli-component detergent granule, provide pHs in this preferred rangeof 8-11.

Preferably the hydratable salt and powdered enzyme are matched for pH,that is the inherent pHs of the enzyme and salt are within a pH unit ortwo. In the composition of this invention, however, such pH matching isnot essential since the moisture absorbing capacity of thepartially-hydrated hydratable salt keeps the moisture away from theenzyme carrier interface, thereby precluding any pH differential in thesalt and enzyme from causing degradation of the enzyme.

The hydratable salt employed as the granular carrier or in the granularcarrier should hold its water of hydration tightly and should readilyaccept more water to fulfill the function required in this invention.Suitable hydratable salts are those having a vapor pressure not greaterthan about 13.15 mm. of Hg at 20 C. and atmospheric pressure. This vaporpressure corresponds to 75% relative humidity as measured over thehydratable salt at the same conditions. Hydratable salts with lowervapor pressures are preferred. Vapor pressure varies with the compoundand with the amount of water of hydration already in the compound. Ananhydrous salt has no vapor pressure. 'In the composition of thisinvention the hydratable salt will always contain some water ofhydration and will have some vapor pressure, depending on how much waterwas used to effect the attachment of the powdered enzyme to the granularcarrier. In the process of this invention either anhydrous orpartially-hydrated hydratable salts can be used as a starting material.

Another important characteristic of the hydratable salt is its capacityto take water of hydration. Preferably this capacity should be in therange of 0.1 to 1.3 lbs. of water per lb. of anhydrous hydratable salt.One pound of anhydrous sodium tripolyphosphate will hydrate about 0.3pound of water.

Examples of suitable water-soluble hydratable salts for use as or in thegranular carrier are as follows.

I. Hydratable salts of an acid with a large, and a base with a small,dissociation constant providing a pH of about 4 to about 7.

II. Hydratable salts of an acid and a base with approximately the samedissociation constant having a pH of approximately 7-8 Na SO 4)4 2 1Ammonium higher fatty acid soaps (C -C 4)2 a tetraammonium ethanehydroxy diphosphonate III. Hydratable salts of an acid with a small, anda base with a large, dissociation constant (e.g. builder salts) having apH of about 8-11 or 12 Nil-51 3010 Na P O trisodium methane or ethanehydroxy diphosphonate, trisodium methane or ethane diphosphonate, tetrasodium ethane, triphosphonate, tetra sodium ethanehydroxytriphosphonate, tetra sodium propane tetra, penta orhexaphosphonate Na CO sodium higher fatty acid soaps (C -C Nazsiogtrisodium nitrilotriacetate di-, triand tetra sodiumethylenediaminetetraacetate The above list is only exemplary. Many otherhydratable salts having the desired pH, vapor pressure and hydrationcharacteristics can be employed. The cations of such hydratable salt canbe alkail metal, such as sodium, lithium or potassium, ammonium,alkanolammonium (e.g. triethanolammonium) and alkaline earth metal suchas calium and barium. Mixtures of such salts can be used.

Many of these hydratable salts vary in hydration capacity, holding from1 to 10 or 12 moles of water.

The preferred hydratable salts are sodium builder salts such as sodiumtripolyphosphate, sodium tetraborate, sodium pyrophosphate. Thesebuilder salts, in any of their partially hydrated forms have a vaporpressure of less than 13.15 mm. of Hg at 20 C. and one atmosphere.Sodium tripolyphosphate, sodium pyrophosphate and sodium tetraboratehave pHs of about 9-10.

With the powdered enzyme attached to the granular carrier, thehydratable salt is preferably not more than hydrated (based on totalhydration capability by weight) in order to provide capacity foradditional hydration during any exposure of the product to freemoisture. Desirably this figure is not more than about 50% of the totalhydration capacity. Generally, about 33% hydration of the totalhydration capacity of the hydratable salt is effected when the powderedenzyme is attached to the granular carrier.

GRANULAR CARRIER The hydratable salt can be used either per se as thegranular carrier or can comprise a portion of a multicomponent granularcarrier. The other components of the granular carrier, when thehydratable salt is only a portion thereof, can comprise diluent salts,organic detergents, detergency builder salts not having the necessaryhydrate characteristics, and other detergent composition components ofthe usual type. The granular carrier of this invention ranges inparticle size from about .075 mm. to about 3.33 mm. (about .003" toabout Mr"). This size range corresponds to granules which pass through 6mesh and remain on 200 mesh (Tyler standard screen). A preferred sizerange is 0.2 mm. to 2 mm. Laundry products, such as conventionalspray-dried detergent granules are in these size ranges which are easyto measure and use without dustiness. The granular carrier preferablyhas a density in the range of from about 0.2 gram/cc. to about 0.8 gram/cc.

The hydratable salts can comprise from 20% to of the granular carrier.Preferably the hydratable salt comprises from 40% to 90% of the granularcarrier in order to provide ample hydration capacity for the carrier andto permit inclusion of other desired components in the granular carrier,such as an organic detergent. When an organic detergent is used with thehydratable salt, particularly a hydratable builder salt, the ratio ofsalt to detergent ranges from 1:4 to 20:1, generally from 1:1 to 9:1.The granular carrier can also contain minor materials: for examplecorrosion inhibitors such as benzotriazole, antiredeposition agents suchas sodium carboxymethyl cellulose, optical brighteners, bactericides,perfumes and dyes. These optional minor components are each commonlyused in amounts up to 2 to 5% by weight of the granular carrier.

The granular carrier with the enzyme attached can be used per se as apre-wash soaking agent or, when the carrier comprises a detergentcomponent such as an hydratable builder salt, as a cleaning agent. Thegranular carrier with attached enzyme can be admixed with other granulardetergent materials of approximately the same particle size and densityto form a multi-component, heavy-duty laundry detergent compositiontailored to have a number of desirable characteristics. In such a case,the granular carrier with enzyme preferably is in an amount ranging fromabout 0.2% to about 30% by Weight of such a multi-component detergentcomposition and is uniformly distributed throughout the detergentcomposition, so that any random sample thereof has about the sameformulation as any other sample. Use of less than about 0.2%carrier+enzyme makes uniformity difficult; more than 30% results in aloss of the advantages of such blending, sometimes calledmaster-batching. If desired, the carrier with enzyme granules can bedyed a bright color and admixed with a white or slightly coloredgranular detergent system to provide an overall composition having adistinctive speckled appearance, in accordance with the teachings ofCanadian Patent 577,479, Britt.

Such an admixture, whether or not with a dye, has the advantage ofpermitting efilcient incorporation of enzymes in a multi-componentdetergent composition wherein the total proportion of granules to betreated with enzyme powder is relatively minor. The launderingadvantages of enzymes are achieved with only a minor amount thereof in adetergent composition. Therefore, it is more efficient to blend a minorproportion of granular carrier having a moderate amount of attachedenzyme with a major proportion of enzyme-free grannies than to attach avery small amount of enzyme to each of the granules in a granulardetergent product. Moreover, the granular carrier is designed to provideimproved stability whereas the detergent composition may not provideconditions for optimum stability.

In a multi-component detergent composition comprising about 0.2% toabout 30% of the granular carrier with attached enzyme, the remaining70% to 99.8% can be granular detergent materials of the conventionaltypes. Generally such materials are mixtures of builders and organicdetergents in weight ratios of 1:4 to 20:1. The builders can be of thehydratable type required for the granular carrier or can be of othertypes such as the polycarboxylate builder salts of U8. Patent 3,308,067,Diehl, issued Mar. 7, 1967.

Whether the hydratable salt comprises all or only a portion of anyparticular granular carrier in the desired size range, it can be in anyparticulate physical form such as granular anhydrous sodiumtripolyphosphate which is relatively dense, or a heat-dried oragglomerated hydratable salt-containing particle which has reduceddensity and expanded surface area formed as a result of a drying oragglomeration step. Conventional spray-dried synthetic detergentgranules can be used since they comprise a significant portion ofhydratable salt, particularly builder salt such as sodiumtripolyphosphate.

A granular carrier which can be used advantageously comprisesspray-dried detergent granules containing sodium tripolyphosphate andanionic organic synthetic detergent in a weight ratio ranging from 8:1to 2:1, containing less than 4%, and preferably less than 2.5% moisture(water or hydration) and being free from the highly alkaline sodiumsilicate commonly used in spraydried synthetic detergent granules.

A low density sodium tetraborate can also be used as a granular carrier.It has an average bulk density of about 0.4 to 0.6 gram per cc. and amoisture (water of hydra tion) content of less than 4%, preferably lessthan 2.5 It is formed by heating sodium borate decahydrate as it passesdownward through a chamber containing heated, upwardly-rising air in theneighborhood of 450 to 550 F.

p 6 ENZYMES The enzymes of this invention are solid catalytically activeprotein materials which degrade or alter one or more types of soil orstains encountered in laundering situations so as to remove the soil orstain from the fabric or object being laundered or make the soil orstain more removable in a subsequent laundering step. Both degradationand alteration improve soil removability. Suitable enzymes are thoseactive at a pH in range of from about 4 to about 12 and preferably inthe pH range of from about 7 to about 11 and at a temperature in therange of from about 50 F. to about 185 F., preferably from 70 F. to F.

White, Handler, Smith, Stetten, Principles of Bio- Chemistry (FirstEdition, 1954), is a valuable reference on enzymes.

Those enzymes which degrade or alter one or more types of soil are largein number and can be grouped into five major classes on the basis of thereactions which they perform in such degradation or alteration. Theseclasses and some of the pertinent sub-classes are described as followsin reaction terms.

I. Enzymes which catalyze the addition or removal of water and therebydegrade soil, especially of a protein type.

A. Hydrolyzing enzymes (hydrolases, e.g., proteases,

esterases, carbohydrases and nucleases) (1) Cleave ester linkages(carboxylic ester hydrolases, phosphoric monoester hydlrolases,phosphoric diester hydrolases).

(2) Cleave glycosides (glycosidases).

(3) Cleave peptide linkages (a-aminopeptide amino acid hydrolases,u-carboxypeptide amino acid hydrolases).

B. Hydrating enzymes (hydrases). (Hydrating enzymes can also be classedas oxidoreductases.)

II. Enzymes which catalyze the oxidation or reduction of a substrate(oxidoreductases). These act on oxizable or reducible soil to degrade itin a manner analagous to an oxidizing bleach or a reducing agent.

A. Transfer a monosaccharide radical (transglycosidases). B. Transfer aphosphoric acid radical (transphosphorylases and phosphomutases). C.Transfer an amino group (transaminases). D. Transfer a methyl group(transmethylases). E. Transfer an acetyl group (transacetylases).

IV. Enzymes which split or form bonds without group transfer(desmosales) and degrade soil such as hydrocarbon soil (e.g. squalene orsterol) to make it more removable.

C-O bonds and V. Enzymes which isomerize molecules (isomerases) andchemically alter a soil such as lipid and carbohydrate so11 to make itmore removable, for example by solubilizmg.

A. Racemases and epimerases. B. cis-trans Isomerases.

C. Intramolecular transferases. D. Intramolecular oxido reductases.

In a few cases a single enzyme may fit more than one of these classes. Anumber of enzyme reactions are not understood clearly enough that theirplace in the above classification can be stated.

In summary the hydrolases, hydrases, oxidoreductases and desmolasesdegrade soil to remove it or make it more removable and the transferasesand isomerases alter soil so as to make it more removable. Of theseclasses the hydrolases are particularly preferred.

The hydrolases catalyze the addition of water to the substrate, i.e.,the substance such as soil with which they interact, and thus,generally, cause a breakdown or degradation of such a substrate. Thisbreakdown of the substrate is particularly valuable in the ordinarywashing procedures, as the substrate and the soil adhering to saidsubstrate is loosened and thus more easily removed. For this reason, thehydrolases are the most important and most preferred sub-class ofenzymes for use in cleaning applications. Particularly preferredhydrolases are the proteases, esterases, carbohydrases and nucleases,with the proteases having the broadest range of soil degradationcapability.

The proteases catalyze the hydrolysis of the peptide I linkage ofproteins, polypeptides and related compounds to free amino and carboxylgroups and thus break down the protein structure in soil. Specificexamples of proteases suitable for use in this invention are pepsin,trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin,BPN, papain, bromelin, carboxy peptidase A and B, amino peptidase,aspergillopeptidase A and aspergillopeptidase B. Preferred proteases areserine proteases which are active in the neutral to alkaline pH rangeand one produced from microorganisms such as bacteria, fungi or mold.The serine proteases which are procured by mammalian systems, e.g.,pancreatin, are useful in acid situations.

Esterases catalyze the hydorlysis of an ester, such as lipid soil, to anacid and an alcohol. Specific examples of the esterases are gastriclipase, pancreatic lipase, plant lipases, phospholipases,cholinesterases and phosphotases. Esterases function primarily in acidsystems.

Carbohydrases catalyze the breakdown of carbohydrate soil. Specificexamples of this class of enzymes are maltase, saccharase, amylases,cellulase, pectinase, lysozyme, oc-glyCOSidaSe and fl-glycosidase. Theyfunction primarily in acid to neutral systems.

The nucleases catalyze the breakdown of nucleic acids and relatedcompounds, degrading residual cell soil such as skin flakes. Twospecific examples of this subgroup are ribonuclease anddesoxyribonuclease.

The enzymes utilized in this invention are generally obtained and storedin a dry, powdered form although they can be utilized in the process ofthe invention in a water slurry. The dry, powdered form is most easilyhandled and generally is more stable than enzymes in a water slurry.Enzymes per se have molecular diameters of from about 30 angstroms toseveral thousand angstroms. However, the particle diameters of theenzyme powder are normally much larger due to agglomeration ofindividual enzyme molecules or addition of inert vehicles such asorganic clays, sodium or calcium sulfate or sodium chloride, duringenzyme manufacture. Enzymes are grown in solution. Such vehicles areadded after filtration of such solution to precipitate the enzyme infine form which is then dried; calcium salts also stabilize enzymes. Theenzyme plus inert vehicle usually comprise about 2% to about 80% enzyme.The enzyme powders of this invention, including the examples, mostly arefine enough to pass through a Tyler Standard mesh screen (0.85 mm.),although larger agglomerates are often found. Some particles ofcommercially available enzyme powders are fine enough to pass through aTyler Standard 100 mesh screen. Generally a major amount of particleswill remain on a 150 mesh screen. Thus, the powdered enzymes utilizedherein usually range in size from about 1 mm. to 1 micron, and mostgenerally from 0.1 mm. to 0.01 mm. The enzyme powders of the exampleshave a particle size in these ranges.

The commercial powdered enzyme products are useful and are generally drypowdered products comprised of about 2% to about active enzymes incombination with an inert powdered vehicle such as sodium or calciumsulfate, sodium chloride, clay or starch as the remaining 98-20%. Activeenzyme content of a commercial product is a result of manufacturingmethods employed and is not critical herein so long as the laundryproduct has the desired enzymatic activity. Many of these commercialproducts contain the preferred proteases as the active enzyme. In mostcases, a subtilisin comprises the major portion of the proteases: otherexamples of hydrolases generally included in commercial products arelipases, Carbohydrases, esterases and nucleases.

Specific examples of commercial enzyme products include: Alcalase,Maxatase, Protease B-4000 and Protease AP, CRDProtease, Viokase,Pronase-P, Pronase-AS and PronaseAF, Rapidase P-2000, Takamine,Bromelain 1:10, HT proteolytic enzyme 200, Enzyme L-W (derived fromfungi rather than bacteria), Rhozyrn P-11 concentrate, Pectinol, LipaseB, Rhozyme PF, Rhozyme I-25; Rhozyme PF and J25 have salt and cornstarch vehicles and are proteases having diastase activity; Amprozyme200.

CRD Protease (also known as Monsanto DA-lO) is a useful powdered enzymeproduct. CRD-Protease is reported to be obtained by mutation of aBacillus subtilis organism. It is about 80% neutral protease and 20%alkaline protease. The neutral protease has a molecular weight of about44,000 and contains from 1 to 2 atoms of zinc per molecule. Its particlesize ranges predominantly from 0.03 mm. to 0.1 mm. The CRDProtease canbe used in an aqueous system having a pH ranging from about 5.4 to about8.9. It can be prepared to range in active enzyme content from 20% to75%. The presence of CaCl in the enzyme powder increases the pH rangeover which this enzyme can be utilized. This enzyme can be utilized inthe composition of this invention with excellent results in washingsolutions at temperatures ranging from about 50 F. to about 150 F. andat lower pHs Suitable for prewash soaking or higher pHs for detergencypurposes.

Pronase-P, Pronase-AS and Pronase-AF are powdered enzyme products whichcan also be used to advantage in this invention. These enzymes areproduced from the culture broth of Streptomyces griseus used forstreptomycin manufacture. They are isolated by the successive resincolumn treatment. The major component of the pronase is a neutralprotease named as Streptomyces griseus protease. This enzyme productcontains a calcium stabilizer salt and is fairly stable over a wide pHrange, e.g., 4 to 10, and is fairly stable over a temperature range of50 F. to 150 F.

Another enzyme product preferred for use in the detergent compositionsof this invention, including a number of the examples, is a proteolyticenzyme, a serine protease, sold under the trade name of Alcalase.Alcalase is described, in a trade bulletin bearing that name, as aproteolytic enzyme preparation manufactured by submerged fermentation ofa special strain of Bacillus subtilis. The primary enzyme component ofAlcalase is subtilisin. In addition to proteolytic activity, Alcalaseexhibits other forms of desirable enzymatic activity. Alcalase is a finegrayish powder having a crystalline active enzyme content of about 6%and a particle size ranging from 1.2 mm. to .01 mm. and smaller, about75% passing through a 100 mesh Tyler screen. The remainder of the powderis comprised primarily of sodium chloride, calcium sulfate and variousinert organic vehicle materials. Alcalase has unusually stableproperties in solution. For example, Alcalase can withstand a pH ofabout 9 at relatively high temperatures, i.e., ISO-170 F., for a shorttime. At 120 F., the activity of Alcalase is virtually unchanged in a24-hour period when held at this pH. Alcalase can be advantageously usedwith soap and detergent compositions of this invention.

The particular enzyme chosen for use in the products and process of thisinvention depends on the conditions of final utility, including carrierpH, composition pH, use pH, use temperanture and soil types to bedegraded or altered. The enzyme can be chosen to provide optimumactivity and/or stability for any given set of utility conditions.

The powdered enzymes are attached to the granular carrier in the laundrycompositions and process of this invention to provide from about .001%to about 20%, preferably .01 to enzyme of the total weight enzyme powderand carrier. When the carrier .with enzyme is uniformly blended withdetergent granules to form a detergent composition, the enzymeconcentration usually ranges from 0.001% to 2%, generally 0.005% to 0.5%of the detergent composition. Taking into account the inert vehicle incommercial powdered enzyme products, the amount of enzyme products(enzyme-l-vehicle) attached to the granular carrier can range up to 40%,preferably up to 20%, of the total weight of enzyme plus carrier.

ORGANIC DETERGENTS The organic detergent compounds which can be utilizedas optional components in the compositions of this invention are soapand anionic, nonioic, ampholytic and zwitterionic synthetic detergentsand mixtures thereof and are exemplified as follows:

(a) Water-soluble soap: Examples of suitable soaps for use in thisinvention are the sodium, potassium, ammonium and alkanol ammonium (e.g.triethanolammonium) salts of higher fatty acids containing from about 10to about 22 carbon atoms. Particularly useful are the sodium andpotassium salts of the mixture of fatty acids derived from coconut oiland tallow, i.e., sodium and potassium tallow and coconut soap.

(b) Anionic synthetic non-soap detergents, a preferred class, can bebroadly described as the Water-soluble salts, particularly the alkalimetal salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl radical containing from about 8 to about 22carbon atoms and a radical selected from the group consisting ofsulfonic acid and sulfuric acid ester radicals. (Included in the termalkyl is the alkyl portion of higher acyl radicals.) Important examplesof the synthetic detergents which form a part of the preferredcompositions of the present invention are the sodium or potassium alkylsulfates, especially those obtained by sulfating the higher alcohols (C-C carbon atoms) produced by reducing the glycerides of tallow orcoconut 'oil; sodium or potassium alkyl benzene sulfonates, in which thealkyl group contains from about 9 to about '15 carbon atoms, includingthose of the types described in United States Letters Patent Nos.2,220,099 and 2,477,383 (the alkyl radical can be a straight or branchedaliphatic chain); sodium alkyl glyceryl ether sulfonates, especiallythose ethers of the higher alcohols derived from tallow and coconut oil;sodium coconut oil fatty acid monoglyceride sulfates and sulfonates;sodium or potassium salts or sulfuric acid esters of the reactionproduct of one mole of a higher fatty alcohol -(e.g., tallow or coconutoil alcohols) and about .1 to 6 moles of ethylene oxide, sodium orpotassium salts of alkyl phenol ethylene oxide ether sulfate with about1 to about 10 units of ethylene oxide per molecule and in which thealkyl radicals contain from 8 to about 12 carbon atoms; the reactionproduct of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil, sodium or potassium salts of fatty acid amide of amethyl tauride in which the fatty acids, for example, are derived fromcoconut oil; and others known in the art, a number specifically setforth in United States Letters Patents Numbers 2,486,921, 2,486,922 and2,396,- 278. Other important anionic detergents, sulfonated olefins, aredescribed in the copending application of Phillip E. Pflaumer andAdriaan Kessler, Ser. No. 561,397 filed June 29, 1966.

(c) Nonionic synthetic detergents: One class can be broadly defined ascompounds produced by the condensation of alkylene oxide groups(hydrophilic in nature) with an organic hydrophobic compound, which maybe aliphatic or alkyl aromatic in nature. The length of the hydrophilicor polyoxyalkylene radical which is condensed with any particularhydrophobic group can be readily adjusted to yield a water-solublecompound having the desired degree of balance between hydrophilic andhydrophobic elements. Another class has semi-polar characteristics.Preferred classes of nonionic synthetic detergents are as follows:

(1) A class of nonionic synthetic detergents under the trade name ofPluronic. These compounds are formed by condensing ethylene oxide with ahydrophobic base formed by the condensation of propylene oxide withpropylene glycol. The hydrophobic portion of the molecule which, ofcourse, exhibits water insolubility, has a molecular weight of fromabout 1500 to 1800. The addition of polyoxyethylene radicals to thishydrophobic portion tends to increase the water solubility of themolecule as a whole and the liquid character of the product is retainedup to the point Where the polyoxyethylene content is about 50% of thetotal weight of the condensation product.

(2) The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to 12 carbon atoms in either a straight chain or branchedchain configuration with ethylene oxide, the said ethylene oxide beingpresent in amounts equal to 5 to 25 moles of ethylene oxide per mole ofalkyl phenol. The alkyl substituent in such compounds may be derivedfrom polymerized propylene, diisobutylene, octene, or nonene, forexample.

(3) Those nonionic synthetic detergents derived from the condensation ofethyleneoxide with the product resulting from the reaction of propyleneoxide and ethylene diamine. For example, compounds containing from about40% to about polyoxyethylene by weight and having a molecular weight offrom about 5,000 to about 11,000 resulting from the reaction of ethyleneoxide groups with a hydrophobic base constituted of the reaction productof ethylene diamine and excess propylene oxide; said base having amolecular weight of the order of 2,500 to 3,000 are satisfactory.

(4) The condensation product of aliphatic alcohols having from 8 to22carbon atoms, in either straight chain or branched chainconfiguration, with ethylene oxide, e.'g., a coconut alcoholethyleneoxide condensate having from 5 to 30 moles of ethylene oxide per mole ofcoconut alcohol, the coconut alcohol fraction having from 10 to 14carbon atoms.

(5) The ammonia, monoethanol and diethanol amides of fatty acids havingan acyl moiety of from about 8 to about 18 carbon atoms. These acylmoieties are normally derived from naturally occurring glycerides, e.g.,coconut oil, palm oil, soybean oil and tallow, but can be derivedsynthetically e.g., by the oxidation of petroleum, or by hydrogenationof carbon monoxide by the Fischer-Tropsch process.

(6) Long chain tertiary amine oxides corresponding to the followinggeneral formula wherein R is an alkyl radical of from about 8 to about24 carbon atoms, R and R are each methyl, ethyl or hydroxyethylradicals, R is ethylene, and n equals from to about 10. The arrow in theformula is a conventional representation of a semi-polar bond. Specificexamples of amine oxide detergents include: dimethyldodecylamine oxide;cetyldimethylamine oxide; bis-(2-hydroxyethyl) dodecylamine oxide;bis-(2-hydroxyethyl)-3-dodecoxy-lhydroxypropyl amine oxide.

(7) Long chain tertiary phosphine oxides corresponding to the followinggeneral formula RRRP O wherein R is an alkyl, alkenyl ormonohydroxyalkyl radical ranging from 10 to 24 carbon atoms in chainlength and R and R" are each alkyl or monohydroxyalkyl groups containingfrom 1 to 3 carbon atoms. The arrow in the formula is a conventionalrepresentation of a semi-polar bond. Examples of suitable phosphineoxides are found in US. Patent 3,304,263 of Feb. 14, 1967 and include:dimethyldodecylphosphine oxide; diethyldodecylphosphine oxide;dimethyl-(2-hydroxydodecyl)phosphine oxide.

(8) Long chain sulfoxides having the formula wherein R is an alkylradical containing from about 10 to about 28 carbon atoms, from 0 toabout 5 ether linkages and from 0 to about 2 hydroxyl substituents, atleast one moiety of R being an alkyl radical containing 0 ether linkagesand containing from about 10 to about 18 carbon atoms, and wherein R isan alkyl radical containing from 1 to 3 carbon atoms and from one to twohydroxyl groups. Specific examples of these sulfoxides are: dodecylmethyl sulfoxide; 3-hydroxy tridecyl methyl sulfoxide; B-methoxytridecyl methyl sulfoxide; 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

(d) Ampholytic synthetic deter-gents can be broadly described asderivatives of aliphatic secondary and tertiary amines, in which thealiphatic radical may be straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to 18 carbon atoms andone contains an anionic water solubilizing group, e.g., carboxy, sulfo,sulfato, phosphato, or phosphono. Examples of compounds falling withinthis definition are sodium-3-dodecylaminopropionate andsodium-3-dodecylaminopropane sulfonate.

(e) Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniumcompounds, in which the aliphatic radical may be straight chain orbranched, and wherein one of the aliphatic substituents contains fromabout 8 to 18 carbon atoms and one contains an anionic watersolubilizing group, e.g. carboxy, sulfo, sulfato, phosphato, orphosphono. Examples of compounds falling within this definition are3-(N,N-dimethyl-N-hexadecylammonio)propane 1 sulfonate and3-(N,N-dimethyl N hexadecylammonio)-2-hydroxy propane-1- sulfonate whichare especially preferred for their excellent cool water detergencycharacteristics. See, for example, Snoddy et al., Canadian Patent708,148 issued Apr. 20, 1965.

PROCESS The laundry composition of this invention is prepared byattaching the powdered enzyme to the granular carrier in the presence ofwater so as to achieve the desirable composition charactetristicsdescribed above. The water employed in such attachment ranges from about1% to about 25% by weight of the hydratable salt employed as or in thegranular carrier. The preferred range is 5l5%. Water in these ranges issufficient to permit efiicient handling of the enzyme and carrier and toaccomrnplish the enzyme attachment satisfactorily. An amount of watergreater than that necesary for these purposes is preferably avoided soas to leave a maximum increment of hydratability in thepartially-hydrated hydratable salt of the granular carrier.

The water can be employed in the process of this invention to effect thedesired enzyme attachment in any of the following methods, all of whichuse agitation:

(1) Water can be used to wet granular carrier followed by promptapplication to the wetted carried granules of the powdered enzyme;

(2) Water can be added to a dry mechanical mixture of the granularcarrier and the powdered enzyme;

(3) The granular carrier, powdered enzyme and water can be addedtogether at about the same time;

(4) Powdered enzyme can be slurried with water and the resulting slurrysprayed onto the granular carrier.

In methods (1), (2) and (3), water is added to the system uniformly,preferably with a fine spray and agitation of the particulate materials.Water can be sprayed while the carrier and enzyme are being agitated ina mixer such as a cement mixer, ribbon blender, rotating drum or panagglomerator, or the Water can be sprayed on the carrier and enzymewhich are in the form of a falling curtain of the dry particulatecomponents. The apparatus described in US. Patent 3,154,496, Roald, ofOct. 27, 1964 can be used. Greater enzyme attachment on a weight basiscan be effected by methods (2) and (3) than by methods (1) and (4). Theadded water of methods (2) and (3) can contain more of the same enzymepowder or a different enzyme powder. When method (4) is employed, theenzyme slurry is applied to the granular carrier, preferably in a finespray while the granular carier is being agitated as for methods(1)-(3).

The amount of water used in the process of this invention, includingmethods (1)-(4), should be sufficient to effect the desired attachment,but without exceeding about preferably 50% of the total hydrationcapacity of the hydratable salt. This amount of water usually rangesfrom 1% to 25%, preferably 5% to 15%, by weight of the hydratable salt.The water for preparing a slurry of powdered enzyme should be sufficientto permit easy handling of the slurry, i.e., to make it pumpable andsprayable. Preferably just enough water is employed for this purpose.The exact amount of water for this purpose will vary somewhat with thetype of enzyme and the type of powder vehicle which might be associatedwith the enzyme and preferably ranges from about 1 to about 3 parts ofwater per part of enzyme product (enzyme+powdered vehicle). More thanabout 3 parts water is usually unnecessary and can result in an undueamount of water in the hydratable salt; less than about 1 part waterpresents spraying problems, e.g. nozzle clogging and pumpingdifficulties.

The attachment techniques should be practiced at ordinary temperatures,i.e., at less than about 150 F., preferably at less than F.

It was surprising that the enzyme powder attaches to the granularcarrier so readily, attaches so firmly and remains stable during andafter the attachment process, even though water is employed to performthe attachment.

UTILITY The laundry composition and detergent of this invention areeffective in cleaning applications in hard and soft water, especially inremoving, or making more removable, soils, stains and other foreignmaterials from textiles and fabrics. For example, they effectively makeremovable or remove the most commonly found soil on garments: skinflakes or other keratin, and lipid mixtures of triglycerides, waxesters, hydrocarbons, free fatty acids, sterols and lipoproteins, e.g,blood, pus, gravy, egg yolk, paint, grease, oil and grass stains If theenzyme employed has amolytic activity, the detergent compositions ofthis invention, including those of the examples, have special usefulnessfor dishwashing and cleaning pots and pans in addition to launderingsoiled fabrics.

EXAMPLES The proportions and percentages of enzyme components given inthe examples do not refer to active enzymes but to powdered enzymeproducts" comprising active enzyme and its powdered vehicle. Alcalase,for example, as described above, contains 6% of active enzyme.

In Examples I-V the enzyme slurry is sprayed onto the granular carrierin a cement mixer with spray nozzles located outside the mixer with thespray being directed inwardly.

In Examples I-V, enzyme activity can be determined by a casein method.According to this test method, a specific amount of casein, aphosphoprotein of milk, is dissolved in water and then a specific amountof the enzyme composition is added to the casein solution. This mixtureis retained at a constant temperature for a standard length of time. Thereaction between the enzymes and the casein is stopped with a strongacid, e.g., hydrochloric or sulfuric acid. The excess casein isprecipitated and then filtered from the mixture. The excess acid istitrated with a strong base. The amount of base required to neutralizethe acid is an indication of enzymatic activity. This method is morefully explained in Glick (Ed), The pH-Stat and Its Uses in Biochemistry,Methods of Biochemical Analysis, volume 4, pages 171-211 (1957) andDixon and Webb (Eds), Enzymes, pages 23-24 :(1958).

In the examples all listings of water in the several formulations referto water in the form of water of hydration either in the granularcarrier and/or the hydratable salts which are admixed with the granularcarrier, e.g., spray dried synthetic detergent granules.

The composition and process of this invention are illustrated by theexamples which follow. Examples are not to be regarded as limiting theinvention. All amounts, percentages and ratios in the specifications andclaims are by weight unless otherwise indicated.

Example I Granular detergent compositions A, B and C are prepared andhave the following formulations:

A. An aqueous slurry containing 38.7% Alcalase and 61.3% water issprayed onto sodium tripolyphosphate in anhydrous granular form having aparticle size ranging from about 0.2 mm. to about 1 mm. The resultinggranular carrier has attached thereto 8% proteolytic enzyme powder, 78%partially hydrated sodium tripolyphosphate and 14% water as water ofhydration. The carrier with attached enzyme is then mechanically mixedwith other detergent ingredients, in the form of spraydried granules ofapproximately the same size as the granular sodium tripolyphosphate, toform Composition A.

B. An aqueous slurry containing 38.7% Alcalase and 61.3% water issprayed onto tetrasodium pyrophosphate in anhydrous granular form havinga particle size ranging from 0.2 mm. to 1 mm. The resulting granularcarrier has attached thereto 10.4% proteolytic enzyme powder, andcomprised 79.0% partially hydrated Na P O and 16.4% water as water ofhydration. The carrier with attached enzyme then is mechanically mixedwith detergent ingredients, in the form of spray-dried granules ofapproximately the same size as the pyrophosphate granules, to formComposition B.

C. Composition C is prepared by dry-mixing the same amount of enzymes asused in compositions A and B with detergent ingredients in the form ofspray dried 14 granules. The powdered enzyme tends to segregate from thespray-dried granules,

In testing Compositions A, B and C for stability, A and B, overall, showsuperior stability, over conditions of time and humidity, relative to C.The powdered enzyme does not segregate significantly in Composition Aand B.

Example II The following granular detergent compositions A, B and C areprepared:

Percent Components Detergent composition A is prepared by dry-mixing theproteolytic enzyme powder with spray-dried detergent granules. Detergentcompositions B and C employ a granular carrier having attached theretothe proteolytic enzyme powder. The carrier with attached enzyme is prepared by spraying an aqueous slurry, containing 34% Alcalase powder ontoanhydrous granular sodium tripolyphosphate of the type used in ExampleI. The carrier with enzyme contains 8.1% Alcalase attached to 76%partially-hydrated sodium tripolyphosphate granu lar carrier, thebalance being water of hydration. The carrier with enzyme ismechanically mixed with other detergent ingredients, which are in theform of spraydried granules of about the same particle size as thecarrier, to form compositions B and C.

In testing Compositions A, B and C for stability, Compositions B and Cdemonstrate stability superior to Composition A. Moreover, segregationof enzyme powder is a problem in Composition A whereas no such problemis faced in Compositions B and C.

Example III The following granular detergent compositions are prepared:

Parts by weight Components B C In compositions A and B, the powderedenzymes (a) and (b) are incorporated into the granular detergentcompositions by dry-mixing. For compositions C and D, the powderedenzymes, (a) and (b) are prepared by spraying aqueous slurriescontaining 35% enzymes and 65% water onto anhydrous granular sodiumtripolyphosphate of the type of Example I. The granular carriers withattached enzyme powder obtained from this operation contained about 4.5%enzyme, 87% partially hydrated sodium tripolyphosphate and 8.5% Water ofhydration and are then mixed into the other granular detergentingredients which are in spray-dried granular form to prepareCompositions C and D. Proteolytic enzyme (a), (Rapidase P-2000manufactured by Rapidase, Seclin, France), and (b), (Protease APmanufactured by Schweizerische Ferment, A.G., Basel, Switzerland),contain approximately onetenth the amount of proteolytic enzymecontained in Alcalase.

Compositions C and D have stability and nonsegregation characteristicsmarkedly superior to Compositions A and B.

Example IV The following granular detergent compositions A, B, C and Dare prepared:

Percent Components A B C D Sodium 010-14 alkyl benzene sulfonate 22.122. 7 22. 7 23. 7 Laurie monoethanol amide 2. 4 2. 5 2. 5 2. 6 Sodiumtripolyphosphate. 42. 3 38. 38. 40. 0 Sodium silicate 5. 9 6. 0 6. 0 6.3 Tetrasodium pyrophosphate 3. 3 Disodium pyprophosphate (NazH Pzov) 2.6 Sodium sultate A 1 .i 5. 4 121). g 13.2 13.2 Proteol tic enz e ca aseWaterj f? 6.8 7.1 7.1 7.4 Miscellaneous detergent additives. Balance to100% For detergent composition A, the enzyme is prepared by spraying anaqueous slurry containing 40% Alcalase and 60% water onto anhydrousgranular sodium tripolyphosphate of the type of Example I (pH of 1%solution 9.7 The granular carrier with attached powdered enzyme powderso obtained contain about 8% enzyme, 80% partially hydrated sodiumtripolyphosphate and 12% water of hydration. The carrier is mixed withother detergent components which are in the form of spray-drieddetergent granules of approximately the same particle size as thecarrier. Composition B is similarly prepared but using anhydrousgranular Na P O of similar particle size (pH at 1% solutionz10z1).

Composition C is prepared in the same manner as A or B; the enzyme issprayed onto anhydrous granular Na I-I P O (pH of 1% solution: 4.2) andvapor pressure of less than 13.15 mm. of Hg at 20 C. and one atmosphere.

In composition D, the enzyme powder is dry-mixed into the detergentcomposition which is in the form of spraydried granules.

The composition of this invention (A, B and C) are superior in stabilityto the dry-mixed composition (D) and do not have the segregationdisadvantage of the drymixed composition.

Example V In this example, an enzyme (Alcalase) is mixed with Water andsprayed onto granular, anhydrous, sodium tripolyphosphate.

More specifically, 258 grams of Alcalase are added to a glass beakercontaining 516 grams of Water at room temperature, 70 F. This mixture isagitated by hand with a spatula until a fluid, homogeneous dispersion isobtained. This dispersion has a viscosity slightly greater than that ofwater and a pH of about 7.0.

Five kilograms of granular, anhydrous, sodium tripolyphosphate having aparticle size distribution ranging from about 100% of the granulesthrough a Tyler Standard 12 mesh screen to about 100% of the granules ona Tyler Standard 100 mesh screen and a density of 0.7 g-ms./cc. areplaced in a baffied cement mixer. The mixer is then started.

An aspirator unit operated by air pressure is placed in the beakercontaining the dispersion of enzyme in water. The dispersion of enzymein water is evacuated from the beaker and sprayed onto the sodiumtripolyphosphate granules. The water is bound to the sodiumtripolyphosphate as water of hydration and the powdered enzyme isattached to the partially hydrated tripolyphosphate granules. Thiscomposition contains about 4.5% attached Alcalase powder and about 9%water of hydration.

361 grams of this granular sodium tripolyphosphate carrier with attachedenzyme are mechanically mixed with 7.5 kilograms of a spray-driedgranular deter-gent of ap- 1 6 proximately the same particle size as thetripolyphosphate carrier containing in parts by weight:

Percent by weight A mixture of 55% sodium tallow alkyl sulfate and 45%sodium linear alkyl benzene sulfonate where- The resulting detergentcomposition has a density of about 0.7 gms./cc., and its recommendedusage in ordinary washing machines is one-half cup. It exhibits superiorstability and laundering characteristics and no segregation problemsrelative to the powdered enzyme.

Example VI Detergent granules were prepared from the followingcomponents:

Parts by weight Anionic paste 35.64 Sodium tripolyphosphate 69.0 Water27.80

Sodium sulfate 4.48

The anionic paste contained, in parts by weight:

Sodium tallow alkyl sulfate 5.06

Sodium linear alkyl benzene sulfonate (see Example V) 4.14 Sodiumsulfate 6.16 Water 20.28

Total 35.64

The components described above were slurried and then spray-dried to amoisture level of 2.18% moisture (water of hydration). The density ofthe resulting granular detergent composition was about 0.40 gms./cc. Theparticle size distribution ranged from a maximum of about 99% through aTyler Standard 14 mesh screen to about 100% retained on a Tyler Standard100 mesh screen.

A slurry containing 1.5 parts of water per part of Alcalase powder wasprepared and 10 parts of this slurry were sprayed onto 92 parts of thedetergent granules. The detergent granules were formed into a fallingcurtain in a pan agglomerator and the water-Alcalase mixture was sprayeduniformly on the falling particles. The water was bound as water ofhydration and the Alcalase was attached to the surfaces of the partiallyhydrated granules. The hydrate vapor pressure of the finished granulescorresponded to a relative humidity of less than 70% at one atmospherepressure and 20 C. The granular carrier with attached powdered enzymecontained, in parts by weight:

Granular carrier (partially hydrated) 92 Alcalase 4 Water of hydration 617 Example VII These components are slurried and then spray-dried to amoisture level of 10.2%. The particle size distribution ranges fromabout 100% through a Tyler Standard 12 mesh screen to about 100% on aTyler Standard 100 mesh screen and the density is about 0.4 gms./cc.

parts of the granular carrier with attached enzyme produced in ExampleVI are mixed with 95 parts of the detergent granules of Example VII.This mixture is suitable for use as a heavy-duty laundry detergent. Itis particularly effective for removing stains of all types on both whiteand colored washable fabrics. The enzyme powder does not segregate fromthe rest of the granular detergent composition.

In the following table, the mixture of Example VII (VII-1, 2 and 3) iscompared to a product of about the same formulation but wherein Alcalasepowder is simply dry mixed with the detergent granules of Example VII toform product #4. The products were packaged in cardboard containers forthis storage test.

In a 20 days period, the dry-mixed detergent composition, Product #4,lost nearly 85% of its enzymatic activity. The detergent composition ofthis invention, VII-1, 2 and 3, showed essentially no less in enzymaticactivity over protracted time periods.

Enzymatic activity was determined by the Azocoll method in this example.This method is based on the release of a water-soluble dye from awater-insoluble protein-dye substrate (Azocoll) by a proteolytic enzyme.The amount of dye released under carefully controlled conditions ismeasured spectrophotometrically. Enzymatic activity is calculated fromthe amount of dye released.

Example VIII grams of granular anhydrous sodium tripolyphosphate havinga particle size ranging from 0.2 mm. to 1 mm. and

a bulk density ranging from .44 to .51 grams per cc.

While the enzyme powder and the granular sodium tripolyphosphate werebeing intimately mixed, 60 kilograms of water were added through theoverhead sprays over a mixing time of 15 minutes. The resulting 500kilograms of granular sodium tripolyphosphate carrier with the powderedenzyme attached contained 12% water as water of hydration, 5 parts ofthe carrier and enzyme can be mixed with parts of the detergent granulesof Example VI to form a detergent composition.

Example IX An enzyme-water slurry of Example VI is prepared and sprayedonto sodium tetraborate granules employing the spraying technique usedin Example VI. The borate granules have a density of 0.5 gm./cc., aparticle size ranging from 1.4 to 0.14 mm. and a moisture content of 2%.The resulting granular carrier with attached enzyme comprised 92partspartially hydrated sodium tetraborate, 4 parts Alcalase and 6 partswater of hydration.

5 parts of the carrier and enzyme of this example are mixed with 95parts of the detergent granules of Example VI. The resulting granulardetergent composition is suitable for use as a heavy-duty laundrydetergent. The granular carriers with attached enzyme do not segregatefrom detergent granules in the packaged product. The stability of theattached enzyme is enhanced.

Example X In this example, results substantially similar to those inExamples VIII and IX are obtained when other enzyme powders aresubstituted, either wholly or in part, for Alcalase to provide partiallyhydrated tripolyphosphate and borate granular carriers with attachedenzymes which are useful laundry compositions having improved stabilityand segregation characteristics. The commercial enzyme powders that canbe substituted for Alcalase to obtain the desirable advantages of thisinvention are Maxatase, Protease B4000, Protease AP, CRD Protease,Viokase, Pronase-P, Pronase-AS, PronaseAF, Rapidase P-2000, Takamine,Bromelain 1:10, HT Proteolytic Enzyme 200, Enzyme L-W, Rhozyme P-llConcentrate, Pectinal, Lipase B, Rhozym PF, Rhozyme I-25, Amprozyme 200.Other classes of enzymes which can be substituted for Alcalase arepepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, ficin,subtilisin, BPN', papain, bromelin, carboxylase, amino peptidase,aspergillopeptidase A, aspergillopeptidase B, gastric lipase, pancreatic lipase, plant lipases, phosphilapases, cholinesterases,phosphotases, maltase, saccharase, amylase, cellulase, pectinase,lysozyme, .a-glycosidase, fi-glycosidase, ribonuclease and desoxyribonuclease.

All of the enzymes of this example have the desired enzymatic activityand are obtained and stored in a dry, powdered form. The enzymes haveparticle size diameters ranging from about 1 mm. to 1 micron, generallyfrom 0.1 mm. to 0.01 mm. The enzymes have an active enzyme content inthe range of about 2% to about 80%.

Example XI When the following hydratable salts, or mixtures thereof aresubstituted, either wholly or in part, for the hydratable salts ofExample X, results similar to those of Example X are obtained. The saltsare employed in an anhydrous or slightly hydrated form at the beginningof the attachment process. Suflicient water is employed to effect thedesired attachment and to partially hydrate the hydratable salt up to 30to 50% of its total hydration capacity. The hydratable salts are: sodiumsulfate, ammonium pyrophosphate, sodium hexametaphosphate, trisodiumethylenediaminetetraacetate, tripotassium N-(2-hydroxyethyl)-ethylenediaminetriacetate, trisodium nitrilotriacetate,tetrasodium ethane-l-hy'droxy-l,1-diphosphonates, trilithium methylenediphosphonate, trisodium ethylene diphosphonate, pentasodiumethane-1,1,2-triphosphonate, disodiumethane-Z-carboxy-1,1-di-phosphonate, dipotassium carbonyl-diphosphonate,tetrasodium ethane-Z-hydroxy-l,l,2-triphosphonate, pentasodiumpropane-1,1,3,3-tetraphosphonate and tri(triethanol ammonium)isopropylidene diphosphonate. The hydratable salts have a particle sizedistribution such that not more than about 30% of the granules areretained on a Tyler Standard 14 mesh screen and no more than 7% of thegranules pass through a Tyler Standard mesh screen.

Generally, the particle size distribution is such that about 100% of thegranules pass through a Tyler Standard 12 mesh screen and about 100% ofthe granules are retained on a Tyler Standard 100 mesh screen.Preferably these hydratable builder salts are employed in a form inwhich average bulk densities range from 0.2 gms./cc. to 0.8 gms./cc,e.g. 0.5 gms./cc.

Example XII When in Example 1, any of the following detergents aresubstituted for the sodium alkyl benzene sulfonate detergentsubstantially similar results are obtained: sodium coconut soap, sodiumlinear alkyl benzene sulfonate having a chain length distribution of 10%C 30% C 35% C12, 16.5% C13, 8% C14 and 0.5 C15, sodium tallow alkylsulfate; the condensation product of one mole of coconut alcohol withmoles of ethylene oxide; the condensation product of one mole of octylphenol with 20 moles of ethylene oxide; the condenstaion product of onemole of coconut alcohol with 20 moles of ethylene oxide;dimethylhydroxydodecylamine oxide; cetyldimethylphosphine oxide;sodium-3-dodecylaminopropionate; and 3- (N,N-dimethyl Ndecylammonio)-2-hydroxypropane-1- sulfonate.

The foregoing description of the invention has been presented describingcertain preferred embodiments. It is not intended that the inventionshould be so limited since variations and modifications thereof will beobvious to those skilled in the art, all of which are within the spiritand scope of this invention.

What is claimed is:

1. A granular laundry composition consisting essentially of a powderedenzyme composition attached to a water-soluble granular carrier whichconsists essentially of 20% to 100% of a partially hydrated hydratablesalt which has a pH in aqueous solution in the range of 4 to 12 and avapor pressure not greater than about 13.15 mm. of Hg when measured atatmospheric pressure at 20 C., which is hydrated not in excess of 90% ofits hydration capacity, and which is selected from the group consistingof alkali metal, alkaline earth metal and ammonium detergency buildersalts having a pH of 4 to 12, fatty acid soaps of to 18 carbon atoms,CaCl and mixtures of said salts, said powdered enzyme composition beingfrom about .001% to about 40% by weight of said laundry composition,consisting essentially of 2% to 80% active enzyme and 98% to 20% inertpowdered vehicle and being attached to said carrier as result ofhydration of said carrier salt, wherein said vehicle consistsessentially of a material selected from the group consisting of calciumsalts, sodium sulfate, sodium chloride, clays and starch and wherein thesaid carrier has a particle size in the range of about 0.075 mm. toabout 3.33 mm.

2. The laundry composition of claim 1 wherein the carrier has a particlesize in the range of 0.2 mm. to 2 mm., the hydratable salt is ahydratable builder salt which has a pH in aqueous solution in the rangeof 8 to 11 and the inert powdered vehicle consists essentially of acalcium salt.

3. The laundry composition of claim 2 wherein the active enzyme is ahydrolase and the hydratable salt is not more than about 50% hydrated,based on its total hydration capacity, and the hydratable builder saltis selected from the group consisting of sodium tripolyphosphate, sodiumpyrophosphate and sodium tetraborate.

4. The laundry composition of claim 3 wherein the hydrolase is selectedfrom the group consisting of proteases, esterases, carbohydrases andnucleases and the hydratable builder salt is sodium tripolyphosphate.

5. The laundry composition of claim 4 wherein the active enzyme is aserine protease and the powdered enzyme composition is in an amountranging from about .001% to about 20% of the total weight of the saidlaundry composition.

6. A granular detergent composition consisting essentially of about 0.2%to about 30% of the granular laundry composition of claim 2 mechanicallyadmixed with from about 99.8% to about 70% of enzyme-free detergentgranules which consist essentially of a water-soluble organic detergentand a water-soluble detergency builder salt, wherein the ratio ofdetergent to builder salt is in the range of 4:1 to 1:20.

7. A process for preparing the laundry composition of claim 3 whichcomprises the steps of (a) wetting said carrier, wherein the saidhydratable salt is initially in an anhydrous or partially hydratedstate, with an amount of water which is from 1% to 25% of the hydratablesalt and insufiicient to hydrate the said hydratable salt more thanabout 50% of its hydration capacity, (b), promptly thereafter saidwetting, applying said powdered enzyme composition to said wettedcarrier, with agitation, to effect the attachment of said enzymecomposition to said carrier and to effect a further partial hydration ofsaid salt.

8. A granular detergent composition consisting essentially of about 0.2%to about 30% of the granular laundry composition of claim 3 mechanicallyadmixed with from about 99.8% to about 70% of enzyme-free detergentgranules which consist essentially of a watersoluble organic detergentand a water-soluble detergency builder salt wherein the ratio ofdetergent to builder salt is in the range of 4:1 to 1:20.

9. A granular detergent composition consisting essentially of about 0.2%to about 30% of the granular laundry composition of claim 4 mechanicallyadmixed with from about 99.8% to about 70% of enzyme-free detergentgranules which consist essentially of an anionic organic syntheticdetergent and sodium tripolyphosphate builder salt wherein the ratio ofdetergent to builder salt is in the range of 4:1 to 1:20.

10. A process for preparing the laundry composition of claim 3comprising the steps of (a) agitating said carrier wherein thehydratable builder salt is in an anhydrous or partially hydrated stateand (b) subjecting said agitated carrier to a fine spray of a mixture ofsaid enzyme composition amd water to effect a partial hydration of saidhydratable salt, thereby attaching said powdered enzyme composition tosaid carrier, the amount of water being from 1% to 25 of the hydratablebuilder salt and insufiicient to hydrate said salt to more than 50% ofits hydration capacity.

11. A process for preparing the laundry composition or claim 5comprising the steps of (a) mixing said powdered enzyme composition inan initially dry state with said carrier wherein the hydratable buildersalt is in an anhydrous or partially hydrated state and (b) subjectingthe resulting mixture to a fine spray of water and simultaneousagitation to etfect a partial hydration of said hydratable salt, therebyattaching said powdered enzyme composition to said carrier, the amountof water being from 1% to 25 of the hydratable builder salt andinsufficient to hydrate said salt to more than 50% of its hydrationcapacity.

12. A process for preparing the laundry composition of claim 5comprising the steps of (a) agitating said carrier wherein thehydratable builder salt is in an anhydrous or partially hydrated state,and (b) subjecting said agitated carrier to a fine spray of a mixture ofsaid enzyme composition and water to effect a partial hydration of saidhydratable builder salt, thereby attaching said powdered enzymecomposition to said carrier, the amount of water being from 1% to 25% ofthe hydratable builder salt, insuflicient to hydrate said salt to morethan 50% of its hydration capacity, and ranging from 1 to 3 parts waterper part of said powdered enzyme composition.

13. A process for preparing the laundry composition of claim 1comprising the steps of (a) mixing said powdered enzyme composition inan initially dry state with said carrier wherein the hydratable salt isin an anhydrous or partially hydrated state and (b) subjecting theresulting mixture to a fine spray of water and simultaneous agitation toeffect a partial hydration of said hydratable salt, thereby attachingsaid powdered enzyme composition to said carrier, the amount of waterbeing in an amount from 1% to 25% of the hydratable salt andinsufficient to hydrate said salt to more than 90% of its hydrationcapacity.

14. A process for preparing the laundry composition of claim 1comprising the steps of (a) agitating said carrier wherein thehydratable salt is in an anhydrous or partially hydrated state and (b)subjecting said agitated carrier to a fine spray of a mixture of saidenzyme composition and water to eifect a partial hydration of saidhydratable salt, thereby attaching said powdered enzyme composition tosaid carrier, the amount of water being from 1% to 25% of the hydratablesalt and insuflicient to hydrate said salt to more than 90% of itshydration capacity.

15. A process for preparing the laundry composition of claim 2comprising the steps of (a) mixing said powdered enzyme composition inan initially dry state with said carrier wherein the hydratable buildersalt is in an anhydrous or partially hydrated state, and (b) subjectingthe resulting mixture to a fine spray of water and simultaneousagitation to eifect a partial hydration of said hydratable builder salt,thereby attaching said powdered enzyme composition to the said carrier,the amount of water being in an amount from 1% to 25 of the hydratablebuilder salt and insuflicient to hydrate said salt to more than 90% ofits hydration capacity.

16. A process for preparing the laundry composition of claim 2comprising the steps of (a) agitating said carrier, wherein thehydratable builder salt is in an anhydrous or partially hydrated state,and (b) subjecting said agitated carrier to a fine spray of a mixture ofsaid enzyme composition and water to effect a partial hydration of saidhydratable builder salt, thereby attaching said powdered enzymecomposition to said carrier, the'amount of Water being from 1% to 25 ofthe hydratable builder salt and insufficient to hydrate said salt tomore than of its hydration capacity.

17. A process for preparing the laundry composition of claim 1 whichcomprises the steps of (a) wetting said carrier, wherein the saidhydratable salt is initially in an UNITED STATES PATENTS 2,717,852 9/1955 Stone.

FOREIGN PATENTS 14,296 1/ 1958 Germany. 265,024 2/ 1927 Great Britain.539,941 9/1941 Great Britain.

OTHER REFERENCES McCutcheon, Synthetic Detergents, McNair-Dorland Co.(1950), p. 230.

LEON D. ROSDOL, Primary Examiner. W. SCHULZ, Assistant Examiner.

US. Cl. X.R. -63, 68; 252-89, 132, 137; 424-94 Dedication3,451,935.Amm'd S. Roalcl, VVeZembeek-O pem Brabant, and Nieolaas T. deOude, Brussels, Belgium. GRAN AR ENZYME-CONTAINING LAUNDRY COMPOSITION.Patent dated. June 24, 1969. Dedication filed Dec. 29, 1969, by theassignee, The Procter (f2 Gamble Company. Hereby dedicates the entireremaining term of said patent to the Public.

[Ojficial Gazette July 21, 1.970.]

